WO1998029414A1 - Fulgimide compounds, use of them, and compositions containing the same - Google Patents

Abstract

Novel fulgimide compounds substituted on the nitrogen atom constituting the imide ring with a phenyl group having an electron attractive group at least at one of the m-positions, which are represented by general formula (I), wherein the group of general formula (a) is an optionally substituted divalent aromatic hydrocarbon or unsaturated heterocyclic group; the group of general formula (b) is an optionally substituted norbornylidene, bicyclo[3.3.1]nonylidene or adamantylidene group; and R2 is an electron attractive group; and the use of them as photochromic material. The fulgimide compounds develop colors in higher densities than those of the photochromic compounds of the prior art.

Description

 Description Fulgimid compounds, their uses and compositions containing them

 The present invention relates to a novel fulgimidinated ^ / having photochromic action and its use. More specifically, a novel fulgimide compound that changes from colorless to colored by the action of light including ultraviolet light such as light from a thick or mercury lamp, the change is reversible, and also has excellent durability, and About its use. Background technology

Photochromism is a phenomenon that has attracted attention for the past several years. When a compound is irradiated with light containing ultraviolet rays, such as sunlight or light from a mercury lamp, the color quickly changes, and the irradiation of light stops. _C) This property, which is a reversible action that returns to the original color when placed in a dark place, is called a photochromic compound, and various structures of ^ / have been synthesized and proposed. However, no special common skeleton is recognized in the structure.

 Against this background, Japanese Patent Application Laid-Open No. Sho 60-155,179 discloses the following "^

[Wherein the group or benzene ring

R ⁴ represents hydrogen, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and Y represents oxygen or / NR (where R represents hydrogen, an aryl group, an alkyl group) Or an alkanolalkyl group). ] A photochromic compound represented by the formula (1) and i) for a ij lens are disclosed, and as specific photochromic ^ /, the following formula ^ / is disclosed in Examples.

Further, the following general formula shown in JP-A-2-28154 and corresponding US Pat. No. 4,882,438

[In the formula, the group X "is a divalent aromatized which may have a substituent.

7-element group or divalent unsaturated heterocyclic group, R ⁵ is a monovalent carbon group or monovalent heterocyclic group, each of which may have a substituent. And

A norbornylidene or adamantylidene group, Y 'is a ^ ^ atom,

Roh _{Ν- R 2, ^ Ν-Α} , -Β - (Α 2) α - (Β 2) ra -R 3, Ν- Α 3 - shows the scale _4] - Alpha ₄ or> _-3,

The fulgide compound or fulgimidized ^ represented by has a stable colorless state in the ¾® form, but develops color immediately upon exposure to sunlight or ultraviolet light, and becomes colorless when the illuminated Ji is stopped. It is a compound that has excellent photochromic properties because it repeats these discolorations with good durability. Here, the fulgide compound or Is a full version of ^^)! As an example, the following formula is disclosed.

Inventive Technology & Technology

 As described above, the fulgide compound or fulmide compound ^ is an excellent photochromic compound in terms of durability and the like, in which coloring and decoloring are reversibly repeated, but these compounds ^! In order to obtain, a large amount was added, and as a result, there was a P-point that the color was not sufficiently decolored at the time of decoloring and the color was reduced with the deterioration in proportion to the added amount. Disclosure of the invention

 Therefore, an object of the present invention is to provide a novel fulgimidation useful as a photochromic compound.

 It is another object of the present invention to provide a fulgimide compound having a sufficiently high density at the time of color development.

 Still another object of the present invention is to provide a fulgimidinated ^ 3 which develops a color sufficiently dense enough for practical use with a small amount of use.

 According to the study of the present inventors, it has been found that the object of the present invention is {β} by a fulgimide compound represented by the following-^ formula (I).

(I)

[In the formula, the following group (a) is a divalent hydrogen aromatic group or a divalent unsaturated heterocyclic group which may have a substituent,

The following groups (b) are a norbornylidene group, a picocyclo [3.3.1] nonylidene group or an adamantylidene group, each of which may have a substituent;

\

 , Τ

R ¹ is a monovalent carbon tzK group or a monovalent heterocyclic group which may have a substituent,

R ² is an electron withdrawing group,

R ³ is an alkyl group, aryl group, amino group, alkoxy group or electron withdrawing group, n is an integer of 0 to 4, and when n is an integer of 2 or more, R ³ is a different atom Or a group. BEST MODE FOR CARRYING OUT THE INVENTION

 In the above formula (I), the group (a) is a divalent aromatic group which may have a substituent, or a divalent unsaturated heterocyclic group, The aromatic group may have at most 5 substituents, preferably up to 3. The aromatic ^ ib7 radical has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. Examples of the ring forming the aromatic S 芳香 ih »include a benzene ring, a naphthalene ring and a phenanthrene ring.

Examples of the unsaturated heterocyclic group include a 5-membered or 6-membered monocyclic heterocyclic group containing 1 to 3 nitrogen atoms, and at least one heteroatom such as a D-yellow atom. Represents a fused heterocyclic group in which a benzene ring or a hexene ring is fused thereto. The ring forming such a heterocyclic group includes, for example, a pyrrole ring, Examples include nitrogen-containing heterocycles such as gin ring, quinoline ring, and isoquinoline ring; ^ ¾heterocycles such as furan, benzofuran, and silane rings; and sulfur-containing heterocycles such as thiophene and benzothiophene rings.

 As described above, the aromatic pentabromide group or unsaturated heterocyclic group represented by the group (a) may contain at most 5, preferably up to 3, substituents. Examples of the substituents include halogen atoms such as fluorine, chlorine, bromine and ¾ ^; hydroxy group; cyano group; nitro group; amino group; carboxyl group; methyl-amino group such as methylamino group and acetylamino group; Alkylamino groups; lower phenolic groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, t-butyl group; halogenated compounds having 1 to 3 halogen atoms such as trifluoromethyl group and 2-chloroethynole group A lower alkyl group; a C1-C4 alkoxy group such as a methoxy group, an ethoxy group, a t-butoxy group; a C6-C0 aryl group such as a phenyl group, a naphthyl group or a tolyl group; a phenoxy group; —Chain with 6 to 14 carbon atoms such as naphthoxy group —Roxy group; C with 7 to 15 carbon atoms such as benzyl group, phenylethyl group and phenylpropyl group Aralkyl groups; aralkyloxy groups having 7 to 15 carbon atoms, such as benzyloxy group and phenylpropoxy group, and alkylthio groups having 1 to 4 carbon atoms. In the case of two R_Ls, these substituents may be of the same kind or-^, and the position is not particularly limited.

 Examples of the group represented by (a) include a halogen atom, a nitro group, a cyano group, an amino group, an alkylthio group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. L may be substituted in each case by at least one atom or group selected from the group consisting of an aryl group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 15 carbon atoms. Divalent aromatic; preferably a ^ ij elemental group or a divalent unsaturated heterocyclic group, 0

 The group represented by (a) contains one nitrogen atom, oxygen atom and one sulfur atom which may be substituted in each case by 1 to 3 of the above substituents. More preferably, it is a 5- or 6-membered monocyclic heterocyclic group.

The group represented by the above (a) is a thiol which may have a substituent. Bases derived from ene or furan are particularly preferred.

 In the general formula (I) according to the present invention, the group (b) means a norbornylidene group, a picilo [3.3.1] nonylidene group or an adamantylidene group, each of which may have a substituent. As the norbornylidene group, a 7_norbornylidene group represented by the following S¾ (b-1) is preferable, and a bicyclo [3.3.1] nonylidene group is a bicyclo [bicyclo] represented by the following formula (b-2). 3.3.1] A 9-nonylidene group is preferable, and an adamantylidene group is preferably a 2-adamantylidene group represented by the following formula (b-3).

The above-mentioned B¾ (b-1), (b-2) and (b-3), which are preferred examples of the group (b), are each a substituted 7-norbornylidene group, a bicyclo [3.3.1 ] 9-nonylidene group and 2 Adamanchiriden _c these 7-norbornene two isopropylidene groups shows the skeleton structure of the group, bicyclo [3.3.1] 9-nonylidene group or 2-Adamanchiriden groups, the upper word Kushi¾ ( hydrogen atom of (b-1), (b-2) or (b-3) may be substituted by a substituent, and the number thereof may be one or more. If it has a substituent, its type, number and position depend on the purpose and It is arbitrarily selected depending on the application. Further, ^^ having a plurality of substituents may be the same substituent, or may be different substituents.

 Examples of the substituents of the 7-norbornylidene group, bicyclo [3.3.1] 9-nonylidene group or 2-adamantylidene group include, for example, a hydroxyl group; a methylamino group; and a carbon number of getylamino ¾ ^:! An alkylamino group having 4 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a t-butoxy group; an aralkoxy group having 7 to 15 carbon atoms such as a benzyloxy group; a phenoxy group, an 11-naphthoxy group; An aryloxy group having 6 to 14 carbon atoms; a methyl group, an ethyl group, a fiber alkyl group having 1 to 4 carbon atoms of t-butyl ^; a halogen atom such as fluorine, chlorine, and bromine; a cyano group; a carboxyl group; An alkoxycarbonyl group having 2 to 10 carbon atoms such as an ethoxycarbonyl group; a halogen-substituted alkyl group having 1 or 2 carbon atoms such as a trifluoromethyl group; a nitro group; a phenyl group; Examples thereof include an aralkyl group having 7 to 9 carbon atoms such as an aryl group, a benzyl group, a phenylethyl group, and a phenylpropyl group.

 Preferred examples of these substituents include a halogen atom, a hydroxyl group, an alkynole group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and a 7 to 9 carbon atoms. Or an aryl group having 6 to 10 carbon atoms.

 Among the above groups (b), a compound having a 2-adamantylidene group represented by the above group (b-1) is particularly preferred in terms of its strong color development.

R ¹ in the above “^ formula (I) is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent.

The carbon ib7 group of R ¹ may be any of aliphatic, alicyclic or aromatic ib * groups, and specific examples thereof include methyl group, ethyl group, propyl group and butyl group. An alkyl group having 1 to 20 carbon atoms, preferably 1 to 6; a cycloalkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms such as a cyclopropyl group and a cyclohexyl group; a phenyl group, a tolyl group, and a xylyl group And aryl groups having 6 to 14 carbon atoms such as naphthyl group; benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl An aralkyl group having an alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as a group, is suitable.

Examples of the heterocyclic group R ^1, a nitrogen atom, three 1 at least one thigh atoms Oyohi sulfur atom such hetero atoms, preferably 1 or 2 comprising 5- or 6-membered ring A monocyclic heterocycle or a condensed complex obtained by condensing with benzene is preferred. Specific examples of such a heterocyclic group include, in addition to the examples of the unsaturated heterocyclic group described in the group (a), a saturated biperidine ring, a piperazine ring, a morpholine ring, a pyrrolidine ring, an indoline ring, and a chroman ring. And other saturated heterocyclic groups. The carbon group or heterocyclic group described above may have a substituent even if it has a substituent. Such a substituent is preferably contained at most 5, and preferably up to 3, with respect to the hydrocarbon group or the heterocyclic group, and specific examples of the substituent have been described as those for the group (a). The same substituents can be exemplified.

Preferred groups for R ¹ are a halogen atom, an alkoxy group having 1 to 4 carbon atoms or a phenyl group, an alkyl group having 1 to 20 carbon atoms; a halogen atom, an alkoxy group having 1 to 4 carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms which may be substituted by a group or a phenyl group; an aryl group having 6 to 10 carbon atoms which may be substituted by a halogen atom or an alkoxy group having 1 to 4 carbon atoms; A condensed heterocyclic group in which a benzene ring is fused to a 5-membered or 6-membered monocyclic heterocyclic group containing 1 to 3 nitrogen atoms, and in particular 1 to 3, especially 1 Particularly, it is a monocyclic heterocyclic group.

Furthermore, R ¹ is particularly preferably an alkynole group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Among them, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms is particularly preferable.

In the above formula (I), R ² is an electron withdrawing group, and is not particularly limited. Examples thereof include a halogen atom, a perhalogenoalkyl group, a cyano group, an alkoxycarbonyl group which may have a substituent, An alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, a nitro group, a sulfonyl group, and a substituent. An alkylsulfonyl group which may have a substituent, a group which may have a substituent L, an arylsulfonyl group or an aryloxycarbonyl group which may have a substituent.

Specific examples of the electron-withdrawing group for R ² include halogen atoms such as fluorine; trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, and nonafnorolobutyl group. A perhalogenoanolequinolene group having 1 to 4 carbon atoms; an alkoxycarbonyl having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbinole group, a butoxycarbonyl group or a t-butoxycarbonyl group; Alkylcarbonyl groups such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, butylcarbonyl group and t-butylcarbonyl group; carbon number 7 to 7 such as benzoyl group and 1-naphthylcarbonyl group; Aryl carbonyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, An alkylsulfonyl group having 1 to 4 carbon atoms such as a tylsulfonyl group; an arylsulfonyl group having 6 to 10 carbon atoms such as a phenylsulfonyl group and a naphthylsulfonyl group; a phenoquinecarbonyl group and a naphthyloxycarbonyl group And an aryloxycarbonyl group having 7 to 11 carbon atoms such as

Further, among the groups represented by R ² , specific examples of the alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group and aryloxycarbonyl group are as follows. Can be exemplified by the same substituents as described in the group (a). And the number may be one or more. Among these substituents, a halogen atom and a cyano group are particularly preferred. The group substituted with the nitrogen atom is preferably a group in which all the hydrogen atoms of the alkoxy group, the alkyl group or the aryl group are substituted with the halogen atom. Examples of such a substituent include those having 2 to 2 carbon atoms such as a trichloromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a heptafluoropropoxycarbonyl group and a nonafluorobutoxycarbonyl group. 5 perhalogenoalkoxycarbonyl group; trichloromethylcarbonyl group, trifluoromethylcarbonyl group, pentafluoroethylcarbonyl group, heptafluoro-propyl propylinole group and nonafluorobutyl carbonyl group A perhalogenoalkylcarbonyl group having 2 to 5 carbon atoms such as a bonyl group; a 7 to carbon atom such as a penfluorofluorobenzoyl group;

Particularly preferred examples of R ² include a cyano group, a fluorine atom, a trifluoromethyl group, and a nitro group.

The "^ groups represented in the formula (I) R ³ is an alkyl group, Ariru group, an amino group, an alkoxy group or an electron withdrawing group, the number of the R ³ (n) is 0 to 4 _c the number of R ³ (n) is 2 or more, R ³ may be the same or different.

As R ³ , an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopropanol group and a cyclohexynole group; a phenyl group, a tolyl group, a xylyl group and a naphthyl group C6-C14 aryl group; C1-C5 alkylamino group such as dimethylamino group, acetylamino group, morpholino group, and piperidino group or a saturated ring group; methoxy group, ethoxy group, t-butoxy group such alkoxy group having 1 to 4 carbon atoms; include the same and electronic absorption attracting group forces as described in the R ^2.

Among the above R ^3, an electron-withdrawing group is preferable, and suitable electron-withdrawing groups include those similar to those described above for R ² .

When R ³ is an electron-withdrawing group, the preferred substitution position on the benzene ring is as follows:

[In the formula, the following groups (a), the following groups (b), R ¹ and R ² have the same meanings as defined in the above-mentioned formula (I).

(b)

 , 2]

The force of substitution at the position indicated by is particularly preferable in terms of color density or conflict.

The number (n) of R ³ is preferably 0 to 4, and a compound in which n is 0 is preferable in terms of obtaining raw materials.

 In the present invention, when a specific example of the formula ^! Represented by the above-mentioned "^ formula (I)" which can be efficiently obtained is given, the following formula ^! Can be exemplified.

 (1) N- (3,1-Cyanophenyl) -1.6,7-dihydro-4-methyl-2- (4, -methoxyphenyl) spirobenzothiophenecarboxyimid-17,2'-tricyclo [3.3 .1.13,7] Decane

 (2) N- (3'-Cyanophenyl) 1-6,7-dihydro-14-methyl-1-2-phenylspirobenzothiophenecarboximidido 7,2'-tricyclo [3.3.1.13,7] decane

 (3) N- (3,1-Cyanophenyl) 1,4-cyclopropyl-6,7-dihydrospirobenzothiophenecarboxyimide 7,2'-tricyclo [3.3.1.13,7] decane

 (4) 6,7-dihydro-4-methyl-1-phenyl-2- (3,1-trifluoromethylphenyl) spirobenzothiophene carboximidido 7,2'-trisic mouth [3.3.1.13,7] decane

 (5) 6,7-Dihydro-4-methyl-N- (3,12-tropheninole) spiroben zothiophene carboximid-1,2'-tricyclo [3.3.1.13,7] decane

 (6) N- (3,, 5'-dicyanophenyl) -6,7-dihydro-4-methyl-2--2-phenylspirobenzothiophenecarboxyimide 7,2'-tricyclo

[3.3.1.13,7] Decane (7) N- (3,1-Fluorophenyl) 1,6,7-dihydro-14-methyl-1,2-phenylspirobenzothiophenecarboximidido 7,2'-tricyclo [3.3. 1.13,7] decane

 (8) N- (3'-Acetylphenyl) 1-6,7-dihydro-14-methyl-2-methylphenylspirobenzothiophenecarboximidido 7,2'-tricyclo [3.3.

1.13,7] Decane

 (9) N- (3'-Benzoylphenyl) 1-6,7-dihydro-4-methyl-12-phenylphenylspirobenzothiophene carboximidido 7,2'-tricyclo [3. 3.1.13,7] Decane

 (10) 6,7-dihydro-4-methyl-N- (3'-methylsulfonylphenyl) -1-2-phenylspirobenzothiophenecarboximido 7,2'-tricyclo [3.3.1.13,7] decane

 (11) 6,7-Dihydro-1-methyl-2-phenyl-1-N- (3,1-phenylsulfonylphenyl) spirobenzothiophenecarboxyimide-1,7,2'-tricyclo [3.3.1.13, 7] Decane

 The fulgimidation represented by the formula (I) of the present invention is present in "^ as a pale yellow or colorless solid at room temperature, and is generally analyzed by the following (A) to (C). By means of ^^ Formula (I) ^ You can sneak in something.

 (A) The ability to know the type and number of protons in a molecule by measuring proton nuclear magnetic spectrum (NMR) τ. That is, δΊ ~

A peak based on an aromatic proton near 8 ppmfi, a broad beak based on a proton derived from a norbornylidene group, a bicyclo [3.3.1] nonylidene group or an adamantylidene group near S 1.2 to 2.5 ppm, δ 1.2 to 4.0 ppm (i) When R ¹ is an alkyl group, the peak value can be calculated based on the alkyl group. Also, by comparing the respective peaks (¾JS) relatively, the number of protons of each bonding group can be determined. it can.

(B) By elemental analysis, the weight percentages of carbon, hydrogen, nitrogen, zeolite, and halogen can be determined. In addition, the weight percent sum of each recognized element must be reduced from 100. Thus, the weight% of oxygen can be calculated. Therefore, it is possible to determine the composition of the corresponding ^^ object.

(0 ⁱ³ c—By measuring the nuclear magnetic spectrum (“C-NMR”), it is possible to know the type of carbon present in the molecule. S Around 27 to 52 ppm, a norbornylidene group, a bicyclo [ 3.3.1] A peak derived from carbon of a nonylidene group or an adamantylidene group, <515 to 35 ppmj, a peak based on the alkyl group when R ¹ is an alkynole group, and an aromatic hydrocarbon near S 110 to 15 Oppm. A peak based on carbon of the group or unsaturated heterocyclic group, and a peak based on carbon with> C = 0 near S 160 to 170 ppm.

 The fulgimide compound of the general formula (I) of the present invention may be produced by any method, regardless of the production method. Preferred and representative methods are described below, but the present invention is not limited to these methods.

 The following general formula (Π)

[Wherein the following groups (a), the following groups (b) and R have the same meanings as defined in the above “^ formula (I)”.

An acid anhydride represented by the following formula [M]

(Wherein R ² , R ³ and n have the same meaning as defined in the above-mentioned “^ Formula (I).)

And then cyclizing the amine compound represented by the formula (1).

 The trace of the suisutsu of the above formula (π) and the amination ^! Of the above formula (m) is preferably carried out in a solvent, and the solvent may be an aprotic polar solvent such as tetrahydrofuran, 1,1, 4 One dioxane and the like.

 In addition, when the hydrate of the above formula (Π) and the aminification of the above Ε¾ (Π) ^ 1 are Sit, the ratio thereof is adopted from a wide range. : 10 to 10: 1, preferably 1: 5 to 5: 1.

 The above reaction is usually performed at a temperature of 25 to 160 ° C and a time of 1 to 24 hours. ¾ίΤ After the completion, the solvent is removed, A is applied with dicyclohexyl carpoimide (DCC), and the ring ih reaction of the obtained compound is performed under the following conditions, thereby obtaining the compound of the present invention. (I).

For the cyclization reaction after the reaction of the above amine compound, a method of heating to a temperature of, for example, 160 to 220 ° C., a method of combining this heating with ultraviolet light, or a method of contacting with Lewis or a medium is suitably adopted. You. Lewis, as the medium, the reduction ^ /, for example, _{SnC 1 4, T i C 1} 4, may be used S bC 1 ₅ or A 1 C 1 ₃ Hitoshiryoku without any limitation. Although the amount of the Lewis solvent is not particularly limited, it is preferably used in the range of usually 0.001 to 1 mol per 1 mol of the compound to be subjected to cyclization it.

 In the above-mentioned production method, the compound of the above formula (II) used as a material can be produced, for example, by the method (F).

That is, the following ^^ formula (Ha)

[In the formula, the following groups (a) and R ¹ have the same meaning as defined in the above-mentioned “^ Formula (I).”

And the following-^ formula (Π b)

And the following groups (b)

 \ Factory

 (b)

 ,

Has the same meaning as defined in the above "^ formula (I),

R ⁶ and R ⁷ represent the same or different alkyl groups having 1 to 6 carbon atoms. The succinic diester derivative represented by the formula (1) can be subjected to a condensation reaction, and the resulting succinic diester derivative can be subjected to the following treatment to obtain the undesired product represented by the above-mentioned formula (^).

In the condensation trace, "The ratio of the carbonyl compound of the formula (na) to the diestenole succinate derivative of the HIS formula (Πb) may be in a wide range, but" ^ is a molar ratio of 1:10 to It is in the range of 10: 1, preferably 1: 5 to 5: 1. The reaction is usually carried out in the range of o ° c to iio ° c, preferably lcrc to: Locrc. Further, RJt is suitable for use in a solvent, and the solvent is preferably an aprotic solvent, and examples thereof include benzene, getyl ether, toluene, and tetrahydrofuran. This condensation is carried out in the presence of a condensing agent such as sodium hydride, t-butoxide, sodium ethylate. Such a condensing agent is usually used in the range of 0.1 to 10 mol per mol of the carbonyl group of formula (na).

 After the completion of the reaction, the obtained dicarboxylic diester is converted to dicarboxylic acid. For this, conditions of hydrolysis in the presence of a base commonly known per se are used. For example, it is performed at a temperature of 0 to 80 ° C. using 10% ethanolano M {7j sodium oxide ””.

 The dicarboxylic acid thus obtained can itself be converted into an acid anhydride according to the method described in the above formula, and can be converted into the hydrate of the general formula (Π). The reaction for producing ugly water is carried out by using a commonly known reagent such as acetic anhydride and acetyl chloride.

 The fulgimide compound of the general formula (I) according to the present invention has a photochromic action by itself, and its durability is excellent in combination with the strength of ultraviolet light, whereby the durability of the photochromic action is improved. It is further improved.

 The fulgimidinated ^ I represented by the above formula (I) of the present invention is well soluble in an organic solvent of "^" such as toluene, chloroform, tetrahydrofuran, etc. Such a solvent is represented by "^ formula (I) When the compound is dissolved, the solvent is almost colorless and transparent, and exhibits a good reversible photochromic action such that the color develops when irradiated with light or ultraviolet light, and returns to the original colorless state immediately when the light is blocked. Such a photomixture fluid can be used for applications such as ^.

 Further, the flumididated ^ I of the general formula (I) exhibits good photochromic properties even in a polymer. Such a polymer can be advantageously used for applications such as photochromic glass and photochromic lens.

As the polymer for dispersing the fulgimidized ^ / of the formula "" (I), any of a thermoplastic resin and a thermosetting resin can be used. Among these, the thermoplastic resin may be any resin that can uniformly disperse the fulgimidized compound of the above formula (I), such as methyl polyacrylate, polyethyl acrylate, and polymethyl methacrylate. , Polyethyl methacrylate, polystyrene, polyacrylonitrile And polymers such as poly (vinyl alcohol), polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, and poly (aryl diglycol carbonate). A polymer obtained by copolymerizing a monomer and the like are preferably used.

 Next, as the thermosetting resin for dispersing the fulgimide 3 of the general formula (I), a known thermosetting resin can be used without any limitation. For example, urethane resin obtained by polymerizing polyfunctional isocyanate with polyfunctional mercapto ^ 5 or polyfunctional hydroxy compound, epoxy resin cured by polyfunctional epoxidation, and curing of multifunctional radical polymerizable monomer Resin.

 The method of dispersing the fulgimide compound of the formula (I) in a polymer is a method of polymerizing a mixture of the fulgimide compound of the general formula (I) and a polymerizable monomer. In the case where the polymer is a thermoplastic resin, the thermoplastic resin and the fluoridized ^ I represented by the formula (I) can be melted at the melting temperature of the thermoplastic resin.

 When mixing the fulgimide compound of the formula (I) with a polymerizable monomer to form a photomixture, the mixing ratio of these compounds is usually The flugimide compound of the formula (I) is preferably 0.001 to: L0 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight.

 ^^ The polymerizable monomer to be mixed with the fulgimide compound represented by the formula (I) should be a radioactive polymer monomer in order to avoid deterioration of photochromic performance due to heavy ^ 14 groups remaining after polymerization. preferable. Examples of the heavy group of the radical polymerizable monomer include a pininole group, an aryl group, an acryloyl group, and a methacryloyl group.In order to obtain a strong photochromic property, an acryloyl group or a methyl chloroinole group is most preferable. .

The following are specific examples of heavy monomers that can be suitably used in the present invention. Examples of polyfunctional radical monomers having a pinyl group / diaryl group include diaryl phthalate, diaryl terephthalate, diaryl isophthalate, diaryl tartrate, diaryl epoxysuccinate, diaryl fumarate, and chlorene. The Polyaryls such as aryl, hexafolenoic acid diaryl, diaryl carbonate, aryldiglycol carbonyl-bonate, trimethylolpropane triallyl carbonate ^ tl; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ) Polyethers such as ether, 1,4-bis. (Methacryloylthiomethyl) benzene, etc., and polyhydric thioacrinoleic acid and polythiothiometrylate ester; divinylbenzene, etc. can be mentioned.

The polyfunctional radical polymerizable monomer having an acryloyl group or a methacryloyl group (hereinafter simply referred to as a polyfunctional (meth) acrylate monomer) is represented by the following formula (IV)

[Where R ^s is a hydrogen atom or a methyl group, and R ⁹ is an alkylene group having 14 carbon atoms or

(However, R ¹⁰ is an alkylene group having 14 carbon atoms, Ha 1 is a halogen atom, and p is an integer of 0 10 and q is an integer of 04 indicating the number of substitution of the halogen atom. And m is an integer of 110. ]

Or a monomer represented by the following general formula (V)

 8

^{_{CH 2 = CCO ~ (R 11}} 0 CH 2) "C-fR 12) t (V)

 4-1

 0

(However, R ^s is a hydrogen atom or a methyl group, R ¹¹ is an ethylene group or a propylene group, r is an integer of 0, 10, s is 0 or 1, and t is 0 2 And R ¹² is a hydrogen atom, a hydroxymethyl group, or a lower alkyl group such as a methyl group or an ethyl group.) Can be mentioned. In the present invention, “(meth) acrylate” is a generic term for methacrylate 5 and acrylate. Further, a monofunctional (meth) acrylate monomer may be added to the above-mentioned polyfunctional radical polymer monomer according to the purpose to obtain a copolymer. Monofunctional (meth) acrylate monomers that can be used for

[However, R ³ is a hydrogen atom or a methyl group, and R ¹³ is a carbon number which may be substituted with a hydroxyl group:! An alkyl group having 4 to 4 carbon atoms which may be substituted with a halogen atom 6 to: an aryl group having L0, and an aralkyl group having 7 to 7 carbon atoms which may be substituted with a halogen atom. ]

In the formula (IV), the alkylene groups represented by R ^g and R ^{10 represented} by R ¹ to R 4 are a methylene group, an ethylene group, a propylene group, an iso-propylene group, a butylene group, an is 0-butylene group, and a trimethylene group. And a tetramethylene group. In the formula (VI), the anoalkyl group having 1 to 4 carbon atoms which may be substituted by the hydroxyl group represented by R ¹³ is a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, The aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom is exemplified by phenyl, naphthyl, chlorophenyl, dichlorophenyl, and trichloro. Examples thereof include a phenyl group, a chloronaphthyl group and a trichloronaphthyl group. Further, the aralkyl group having 7 to 7 carbon atoms which may be substituted with a halogen atom includes a benzyl group, a phenyl group, and a benzyl group. Group, bromobenzyl group, trichlorobenzyl group, and tribromobenzyl ^ !.

Specific examples of compounds that can be suitably used as the polyfunctional (meth) acrylate monomer represented by the above-mentioned formulas (IV) and (V) include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethylene glycol (meta) Acrylate, tetraethylene glycol (meta) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol Mono (meth) acrylate, polybutyleneglycol mono (meth) acrylate, 1,6-hexanedi-di (meth) acrylate, neopentylglycol di (meth) acrylate, 2,2'-bis (4— Acrylic acid and methacrylic acid esterification of propane ^ ;, 2,2'-bis (4-methacryloyloxy-polyethoxyphenyl) propane acrylic acid and methacrylic acid Acrylic acid and methacrylic acid ester compounds of 2,2'-bis (4-methacryloyloleoxybutoxypropoxyphenyl) propane, 2,2'-bis (4-methacryloyloxy-polypropoxyfif) Enyl) Esterification of propane with acrylic acid and methacrylic acid ^ !, 2, 2'-bis [(3,5-dibromo-14-methacryloyloxyxetoxyphenyl) propane acrylic acid and methacrylic acid esterification ^! And trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. One of these polyfunctional (meth) acrylate monomers may be used as a mixture, or a mixture of two or more thereof may be used.

 Specific examples of the monofunctional (meth) acrylate monomer represented by the general formula (VI), which can be suitably used as a monomer, include methyl (meth) acrylate and methyl (meth) acrylate. ) Acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, etc. You. These monofunctional (meth) acrylate monomers may be used alone or in combination of two or more.

When α-methylstyrene dimer is added to the photochromic yarn containing the “^ formula of the formula (I) and heavy ^ ft monomer, the β ^ property at the time of curing is improved and the yield is further increased. Good polymer can be obtained, and it has polymerizability such as α-methylstyrene. By adding a monofunctional radically polymerizable monomer, the properties are further improved. Therefore, as photochromic products, 0.1 to 2 parts by weight of methyl styrene dimer, 0 to 15 parts by weight of α-methylstyrene, and 100 to 100 parts by weight of heavy ft monomer Flugimidation of the general formula (I) ^ 50 · 001 to 10 parts by weight of a string is preferable. In addition, when a heavy ft monomer having at least one epoxy group in one molecule (hereinafter simply referred to as an epoxy monomer) is added to the photochromic substance, the fulgimide of the general formula (I) is obtained. It is preferable because the durability of the chemical compound I can be improved.

 As the epoxy monomer, a compound having at least one epoxy group and a radical polymerizable group in one molecule is preferably used. Examples of the radical heavy group include "^ include a vinyl group, an aryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group is preferable for obtaining a good photochromic property. The epoxy monomer which can be preferably used in the present invention is represented by the following formula (^)

(However, R ⁵ and R ¹⁶ are each a hydrogen atom or a methyl group,

R ¹⁴ and R ¹⁵ are each an alkylene group having 1 to 4 carbon atoms which may be substituted with the same or different hydroxyl groups, or

Wherein u and V are each independently 0 or 1. ).

Alkylene group represented by R ¹⁴ and R ¹⁵ in the above formula include methylene group, ethylene group, propylene group, heptylene group, trimethylene group or tetramethylene it is possible example Shimesuru. These groups may be substituted with a hydroxyl group. No.

 Specific examples of the epoxy monomer that can be suitably used in the present invention include glycidyl (meth) acrylate, 9-methyldaricidyl (meth) acrylate, and bisphenol A-monoglycidyl ether (meth). Acrylate, 4-glycidyloxybutyl (meth) acrylate, 3- (glycidyl-2-oxyethoxy) -1-hydroxypropyl (meth) acrylate, 3- (glycidyloxy-1-isobroviroxy) Examples thereof include methacrylate compounds and acrylate compounds such as 2-hydroxypropyl (meth) acrylate and 3- (glycidyloxy-2-hydroxyproviroxy) -1-hydroxybutyrate (meth) acrylate. Of these, glycidyl (meth) acrylate is preferred in order to further improve the durability of the photochromic action.

 The epoxy monomer is usually a heavy monomer, preferably a radical heavy ft monomer, and more preferably 100 parts by weight of a polyfunctional and Z- or monofunctional (meth) acrylate monomer. Adding up to 30 parts by weight and further from 1 to 0 parts by weight can improve the durability of the photochromic action of the fulgimide compound of formula (I) and decrease the heat resistance. It is preferable because the force can be prevented.

 The fulgimidization of the above-mentioned formula (I) is a conversion from purple to blue ^ 3. In combination with other known photochromic compounds, a gray, which is preferred as a typical photochromic lens, A photochromic yarn that develops a neutral color such as amber and brown can be used as the photochromic mixture ^! To be combined is preferably a spirooxazine compound ^ or a chromene compound ^.

The above-mentioned chromene formation ^ has a chromene skeleton and is known as photochromic ^! What like even ₀ it is monkey in which fine without limitation {Migiwaki ~ ^ ¾ formula chromene of which is shown at (VDI) ^ is preferably used.

[Wherein, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^2C ′ are the same or different hydrogen atoms, alkyl groups, aryl groups which may be substituted, substituted amino groups, unsaturated heterocyclic groups, Or a saturated heterocyclic group, wherein R ¹⁹ and R ²⁰ may be "^ to form a ring;

The group represented by is a divalent aromatic: ^ bj-substituted or optionally heterocyclic group which may be substituted. ]

The alkyl groups represented by R ¹⁷ , R ¹³ , R ^19, and R ²⁰ in the contact type (VDI) are methyl, ethyl, and propyl ^! You can power. Examples of the aryl group include a phenyl group and an aryl group having 6 to 10 carbon atoms such as naphthyl ^ !. Examples of the substituted aryl group include a 4-methoxyphenyl group and a 3-fluoro-4-methoxyphenyl group. We can raise the power. Examples of the substituted amino group include an amino group in which at least one hydrogen atom has been substituted with a methylamino group, an ethylamino group, a dimethylamino group, a phenylamino group, an alkyl group of naphthylamino or an arylene group. Examples of the unsaturated heterocyclic group include one or two nitrogen atoms, atoms or hetero atoms as hetero atoms such as a pyrrole ring, a pyridine ring, an indoline ring, a furan ring, a benzofuran ring, a thiophene ring, and a benzothiophene ring. A monovalent group derived from a 6-membered ring, or a benzothiophene ring, a tetrahydrobenzothiophene ring, a benzofuran ring, a tetrahydrobenzofuran ring, etc., derived from a condensed ring thereof with a benzene ring or a cyclohexane ring The monovalent group can be mentioned. The saturated heterocyclic group includes a nitrogen atom such as a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and a 5- to 6-membered ring containing one or two oxygen atoms or hetero atoms as hetero atoms. The ability to cite a derived monovalent group <can.

In the above-mentioned formula (Vffl), the ring formed by R ¹⁹ and is “^” includes a norbornylidene group and a bicyclo [3.3.1] 9-nonylidene bond. In the general formula (),

Examples of the divalent aromatic carbon ib * element group or unsaturated heterocyclic group represented by are divalent groups derived from one benzene ring or two to three condensed rings thereof. As a divalent unsaturated heterocyclic group, a 5- to 7-membered ring containing one or two nitrogen atoms, ^^ atoms or io atoms as hetero atoms, or a condensed ring thereof with a benzene ring or a cyclic hexane ring Examples thereof include a divalent group derived from a fused ring.

 Specific examples of the divalent aromatic carbon group include groups having 6 to 14 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and the like. Specific examples of the divalent unsaturated heterocyclic group include a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrroyl ring, an indole ring, a furan ring, a benzofuran ring, a tetrahydrobenzozofuran ring, a thiophene ring, and a benzothiophene ring. And a group having 4 to 9 carbon atoms derived from a ring or a tetrahydrobenzothiophene ring. The substituent of each of these groups is not particularly limited, and examples thereof include a halogen atom such as fluorine, chlorine, bromine, and iodine; an alkyl group having 1 to 20 carbon atoms of a methyl group and an ethyl group: a methoxy group, an ethoxy group, and the like. C1-C20 alkoxy group: phenyl group, tolyl group, xylyl ^ carbon number 6-: L0 arylene group; C1-C14 alkoxyaryl group (C1-C4 alkoxy group An amino group; a nitro group; a cyano group; a monovalent saturated heterocyclic group such as a pyrrolidine ring, an imidazolidin ring, a piperidine ring, a virazine ring, or a morpholine ring. The ring ¾ ^ can be exemplified.

Particularly preferred chromene compounds in the present invention are those represented by the general formula (VI), wherein both R "and R are hydrogen atoms, and R ² ':' is the same or different. An alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms or an unsaturated heterocyclic group, or a bicyclo [3.3.1] 9-nonylidene group or A two-ylidene group,

Is a group derived from a naphthalene ring which may be substituted with an alkoxy group having 1 to 20 carbon atoms or a saturated heterocyclic group having Hffi.

 Specifically, the following compounds can be exemplified by the chromene formation / which can be performed in the present invention.

 (1) Spiro (Norbornane-1,2 '-(2H) Benzo (h) chromene) (2) Spiro (Bicyclo [3.3.1] Nonane-1,9,2'-(2H) Benzo (h) Cumen)

 (3) 7'-methoxyspiro (bicyclo (3.3.1) nonane-1,2 '-(2H) benzo (h) chromene)

 (4) 7'-methoxyspiro (norbornane-1,2 '-(2H) benzo (h) chromene)

 (5) 2,2-Dimethyl-7-octoxy (2H) benzo (f) chromene

 (6) 2,2- (2 'difuryl) (2H) benzo (f) chromene

 (7) 2,2- (Feneru 2'-furyl) (2H) benzo (f) chromene

(8) 9-morpholino 2,2-difuunil (2H) benzo (f) chromene (9) 9-morpholino-1,2,2-bis (3-fluoro-4-methoxyphenyl) (2H) benzo (f) chromene

 (10) 2,2-— ((2,1- (3'-Fluoronaphthyl) -1-2'-Chenyl) (2H) benzo (f) chromene

As the spiroxazine compound which can be combined with the fulgimidinated compound of the formula (I), a known compound having a spiroxazine skeleton and having photochromic properties can be used without any limitation. For example, the following general formula (Spiroxazinated ^! Indicated by DO is preferably shelved.

[However, R ²¹ , R ²² and R ²³ are the same or different alkyl groups, cycloalkyl groups, alkyloxyalkyl groups, alkoxycarbonyl groups, alkoxycarbonylalkyl groups, aryl groups, aralkyl groups, alkylthioalkyl groups a Ashiru group or Ashiruokishi group, R ²² and R ²³ may form a connexion ring such together, both R ^{2 1,} R ²² and R ²³ may have a substituent,

Also,

Is a divalent aromatic group or a divalent unsaturated heterocyclic group which may be substituted, and

The group represented by is a divalent aromatic group which may be substituted, or a divalent hydrogen atom or a divalent unsaturated heterocyclic group. ]

In the above-mentioned “^ formula (K), examples of the alkyl group represented by R ²¹ , R ²² and R ²³ include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, an isopropyl group and a neopentyl group. ^^ Examples include an alkyl group having a number of 1 to 5. Examples of the aryl group include a phenyl group and an aryl group having 6 to 10 carbon atoms of naphthyl. Propyl, cyclobutyl and cyclohexyl ¾ ^ are cycloalkyl groups having 3 to 8 carbon atoms Examples of the alkyloxyalkyl group include a methyloxymethyl group and a methyloxymethyl group. And alkyloxyalkyl groups having 2 to 10 carbon atoms, such as a group and an ethyloxymethyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an alkoxycarbonyl group having 2 to 2 carbon atoms of ethoxycarbonyl. Examples of the alkoxycarbonylalkynole group include a methoxycarbonylmethyl group, an ethoxycarbonylmethynole group, and an alkoxycarbonylalkyl group having 3 to 15 carbon atoms of methoxycarbenyletinole. Examples of the aralkyl group include a benzyl group, a phenylethyl group and an aralkyl group having 7 to 20 carbon atoms of naphthylmethyl. Examples of the alkylthioalkyl group include a methylthiomethyl group, a methylthioethyl group, and an alkylthioalkyl group having 2 to 10 carbon atoms of ethylthiomethyl ^. Examples of the acetyl group include an acetyl group and an acetyl group having 2 to 10 carbon atoms of ethyl carbonyl. Examples of the alkylcarbonyl group include a methylcarbonyl group and an ethylcarbonyl group having 2 to 10 carbon atoms.

 Examples of the substituent of each group described above include a halogen atom, a nitro group, a cyano group, and a plurality of groups.

In the above "^ formula (K),

Each of which may be substituted, represented by a divalent fragrance! The hydrogen hydride group or the divalent unsaturated heterocyclic group is the same as the group in the above-mentioned formula (Cor).

In the general formula (IX),

The optionally substituted divalent hydroaromatic group or divalent unsaturated heterocyclic group represented by is the same as in the above-mentioned formula (基).

These substituents are described as the substituents of the group in the above "" ^ formula (). Can choose the group that

_ _NR 24 _R 25

(However, R ²⁴ and R ²⁵ may be an optionally substituted alkyl group, alkoxy group or aryl group, and R ²⁴ and R ²⁵ may be bonded to each other and cyclized to form a nitrogen-containing heterocyclic ring. .)

Are preferred.

In the spirooxazine compound represented by the above-mentioned “^ formula (K), R ²¹ is an anoalkyl group or an alkoxycarbonylalkyl group, and R ²² and R ²² are an alkyl group or a cycloannoleyl group that forms a ring around the alkyl group. ,

Is preferably an aromatic group which may or may not be completely substituted. An aromatic carbon group which may or may not be substituted is an alkyl group or a halogen atom, especially an aromatic group which is completely or completely substituted by a halogen atom, particularly fluorine;

Is preferably a naphthalene ring substituted with an optionally substituted aromatic group, particularly an amino group.

 Specific examples of the spiroxazine compound that can be suitably used in the present invention include the following compounds.

 (1), 5'-Dimethyl-1-6'-Fluoro-6 "-Morpholinodispiro (Six Methylhexane 1,3 '-(3H) India 1-Lu 2'-(2H), 3"-(3H) Ft (3,2-a) (1,4) oxazine

(2) 6'-Fluoro-methoxycarbonyl-2-ethyl-8 "-methoxy-6" -piperidinodispiro (cyclohexane-1,3,1- (3H) India 1-ru 2 '-(2H), 3 " — (3 H) naphtho (3, 2— a) (1,4) oxazine (3) 1- (2- (dioxane-2-yl) ethyl) —6 '—fluoro-6 "-(4-methylbiperazino) dispiro (cyclohexane-1, 3'-(3Η) indole-1 2 '— (2Η), 3, '1 (3Η) naphtho (3, 2—a) (1,4) oxazine

 (4) 5 ', 7' -Difluoro-methyl-1 6 "-morpholinodispiro (Sik Mouth hexane 1, 3 '-(3H) India 1 2'-(2H), 3"-(3H) (3,2_a) (1,4) oxazine

 (5) Γ —isobutyl-5 ′ —methyl-6 ′ —fluoro-6 ″ —morpholinodispiro (cyclohexane-1,3 ′ — (3H) indole-1 2 ′ — (2H), 3 ”naphth (3 , 2— a) (1,4) oxazine

In the photochromic product of the present invention, the fulgimidization of the formula (I), the chromeneation of the formula (ring) ^ / and Z or the spiroxazinezine of the formula (IX) are respectively represented by the following formulas: one or no problem even if a mixture of two or more photochromic of ^ the mixing ratio of these various especially |. Personal Protection for First Aid or Rescue Personnel Sarezu, good if ^^ appropriately in consideration of the respective Fotoku port Mick of ^), ₀ ^ Specifically, the above-mentioned «???????????????????????????????????????????????????????? It is preferably contained in an amount of 0.001 to 10 parts by weight, more preferably 0.01 to 0.2 part by weight, based on 100 parts by weight of the monomer.

 In addition, when various photochromic compounds are mixed as described above, the durability of each photochromic compound differs, so if the obtained photochromic cured product is used for a long time, the color tone before and after ffiffl will shift, so-called `` color shift ''. May occur. It is Rikikawano to avoid such problems by adjusting the types and mixing ratios of various types and various types ^). For example, the following items can be obtained.

 [1] (A) and (B) below

(A) 100 parts by weight of a radical fe monomer represented by the formulas (IV), (V) and (VI) (B) 0 to 30 parts by weight, preferably 1 to 30 parts by weight of the epoxy monomer represented by the formula (^)

100 parts by weight of heavy monomer

 [2] (C), (D) and (E) below

 (C) The flugimidized compound represented by the above-mentioned formula (I) ^ 0.01 to 0.05 parts by weight, preferably 0.01 to 0.03 MM part

 (D) The above-mentioned ^^ formula (W) Chromene ^) 0.01 to 0.2 parts by weight, preferably 0.01 to 0.1% by weight

 (E) Spiroxazinated compound represented by the formula (IX) ^! 0.03 to 0.1 part by weight, preferably 0.03 to 0.06 part by weight

A thread product comprising the photochromic ligated product of (C), and further having a weight ratio [(C) / (E)] of the compounding amount of (C) to the compounding amount of (E) of 1 or less.

 Further, as a method of eliminating the “color shift”, there is a method of adding ultraviolet light. As the UV light, the UV light added to various plastics can be used without any limitation. In the present invention, considering the improvement of the durability of the photochromic compound, among various types of ultraviolet light, benzotriazole-based ultraviolet absorbers, quencher of singlet state, hindered amine agent ("^ (Including Mitsuyasu having a hindered amine structure and a hingodophenol structure).

As the above-mentioned benzotriazo monouret type ultraviolet absorber, benzotriazo mono-b-grade UV-absorbing compound of ^ D can be used without any limitation. For example, the following "^ formula (X The benzotriazonole type ultraviolet absorber shown in) can be used on the thigh.

[However, R ²⁶ and R ²⁷ are the same or different hydrogen atoms, alkyl groups, aryl groups and aralkyl groups, respectively, and R ^2S is a hydrogen atom or a chlorine atom. ] One- In the above ^^ formula (X), the alkyl group represented by R ² ' ^s and R ²⁷ includes a methyl group, a butyl group, a sec_butyl group, a t-butyl group and the like. Alkyl groups can be mentioned. Examples of aryl groups include aryl groups having 6 to 20 carbon atoms, such as phenyl groups, butylphenyl groups, sec-butylphenyl groups, and t-butylphenyl groups. Examples of the aralkyl group include a benzyl group and a phenylalkyl group having 7 to 20 carbon atoms.

Formulas (X) in which R ²⁶ and R ²⁷ are the same or different from each other in the formula (X), are alkyl groups having 1 to 5 carbon atoms, particularly methyl groups, t-butyl groups. A t-amyl group, an arylene group having 6 to 15 carbon atoms, particularly a methylphenyl group, a t-butylphenyl group, a t-octylphenyl group, or an aralkylene group having a carbon number of 7 to 15, particularly a benzylinole group, α, 1-dimethylbenzyl It is a compound that is a group.

 Specific examples of the benzotriazole-based ultraviolet absorber that can be suitably used in the present invention can exemplify the following compounds.

 (1) 2- (5-Methyl-1-hydroxyphenyl) benzotriazole [Product name: Tinuvin II: Nippon Ciba Geigy Co., Ltd.

 (2) 2- [2-Hydroxy-1,3,5-bis (α, α-dimethylbenzyl) phenyl] -2Ηbenzotriazole [Product name: Tinuvin 234, manufactured by Nippon Ciba Geigy Co., Ltd.]

 (3) 2— (3,5-g-t-butyl-2-hydroxypheninole) benzotriazole [Product name: Tinuvin 320, manufactured by Nippon Ciba Geigy Co., Ltd.]

 (4) 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -15-chlorobenzozotriazole [trade name: Tinuvin 326, manufactured by Nippon Ciba-Geigi Co., Ltd.]

(5) 2- (3,5-Di-tert-butyl-2-hydroxyphenyl) 15-chlorobenzototriazole [Product name: Tinuvin 327, Nippon Ciba Geigy Co., Ltd. ¾h] (6) 2- (3, 5-G-t-amyl-1- (2-hydroxyphenyl) benzotriazole [Product name: Tinuvin 328, manufactured by Nippon Ciba Geigy Co., Ltd.] (7) 2- (2'-Hydroxy-5'-t-octylphenyl) benzotriazole (trade name: Tinuvin 329, manufactured by Nippon Ciba-Geigi Co., Ltd.)

 The amount of the ultraviolet absorber is preferably 0.005 to 0.1 part by weight, more preferably 0.01 to 0.05 part by weight, based on 100 parts by weight of the heavy monomer.

Next, examples of a quencher of a singlet-type ion, which is an ultraviolet ray, include a complex of Ni ²⁺ and an organic ligand, conooctyl (m) -tris-tri-n-butyldithiolbamate, iron ( m) —Diisopropyldithiolbamate and Cobalt (π) —diisopropyl pyridithiocanolebamate. Among these singlet-state ^^ extinctions, the complex power of Ni ²⁺ and the ligand is particularly favorable. Specific examples of such a complex include, for example, the complexes u-1 to u-4 described above. u— 1

[2,2'-Chobis (4- (1,1,3,3-tetramethylbutyl) phenolate) butylamine] Nickel

u-2

Nickel bis [o-ethyl (3,5-di-ert-butyl-4-hydroxybenzyl)] phosphonate

u-3

Nickel-dibutyldithiocarbamate

 u-4

Bis [2,2'-thiobis-4-1 (1,1,3,3-tetramethylbutyl) phenolate] nickel

 Other examples include Ni complexes marketed by Hueguchi Corporation under the trade names UV-CHECK AM-105, UV-Check AM126, and UV-Check AM205.

 Specific examples of the above-mentioned hindered amines which are suitable as UV stabilizers include the following compounds represented by u-5 to u-12.

 u-5

u— 6

u-7

u-8

u-9

u 0

Five

Sum 10 isorb LS-2000 and LS-2001 (both are trade names) manufactured by Co., Ltd.

The method for producing a photochromic product of the present invention is not particularly limited, and the components may be mixed in any order.

 The hard it method for obtaining a cured product from the photochromic material of the present invention is not particularly limited, and a known curing method can be employed. The polymerization can be carried out by using a shelf of various radical polymerization initiators such as various peroxides, azotized ^ 3, or by irradiating ultraviolet rays, α rays, / S rays, α rays or the like, or by using both. (As an example of a typical polymerization method, the photochromic composition of the present invention, in which a radical cane polymerization initiator is contained in advance, is injected between the elastomer gaskets or the molds formed by the spacers. Casting polymerization can be adopted which is performed after the polymerization is performed.

 The radical polymerization initiator is not particularly limited, and examples of typical radical polymerization initiators that are capable of ^ ffl include known compounds such as benzoyl peroxide, p-chlorobenzene oxide, decanol peroxide, and lauroyl peroxide. Diarynoperoxides such as tert-butylperoxide, acetylbenzene, etc .; t-butylperoxy-12-ethylhexanate, t-butylperoxyneodecanet, cumylperoxynedecanenet, t-butylperoxybenzoate, t-butylperoxide Peroxyesters such as oxoisobutyrate, 1,1.3,3-tetramethylbutynolepropoxy-1-ethylhexaneate; diisopropylpropylperoxycarbonate; Percarbonates such as carbonates; azobisisobutyronitrile, etc. § zone of ^! ^ A can be force mentioned. Among them, t-butyl vaxoxy neodecaneate, t-butyl vaxoxy neodecaneate / 1-butyl vaxoxy neobutarate, t-butyl vaxoxy neodecaneate Z1,1,3,3-tetramethyl A combination of butyloxyl-2-ethylhexanate is preferred in terms of polymerization efficiency and hardness of the polymer.

 In the present invention, the photochromic effect of the fulgimidization of ^^ formula (I) ^ / is a conventionally known fulgidification ^! And ^^ are significantly improved in color development as compared to fulgimidation ^.

Therefore, the fulgimidized ^ / of the present invention is widely used as a photochromic material. For example, various words such as various memory materials, copying materials, E (¾l) ffl photoconductors, negative tubes, Si materials, laser materials, holographic materials, etc. In addition, the photochromic material using the compound of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a meter, a ^, etc. For example, a photochromic lens In the case of (2), there is no particular limitation as long as uniform light control performance can be obtained. Specifically, for example, a polymer film obtained by uniformly dispersing the photochromic material of the present invention in a lens is used. Sandwiching, or dissolving this conjugate in silicone oil, for example, at 150 to 200. Impregnating the lens surface with C for 10 to 60 minutes, In addition, there is a method in which the surface is coated with a curable substance to form a photochromic lens, etc. Furthermore, a method in which the above-described polymer film is formed into a lens surface, and the surface is coated with a curable l® to form a photochromic lens. Further, the photochromic ^ / of the present invention can be dispersed in a monomer capable of forming an organic lens in advance, and then polymerized and cured to form a photochromic lens.

 Hereinafter, the ability to explain the present invention in more detail by way of Example H The present invention is not limited to these examples. Note that “parts” in the examples is parts.

Male example 1

A solution was prepared by dissolving 15.1 g (0.065mo1) of 4-acetyl-2- (4'-methoxyphenyl) thiophene and 20.0g (0.065mo1) of getyl 2-adamantylidene succinate in 20 Om1 of toluene. . Next, in a solution in which 5.6 g of sodium hydride was dispersed in 200 ml of toluene, the solution temperature of the toluene solution was kept at 0 ° C. or lower, and the mixture was vigorously stirred for 10 hours. After hydrolyzing with a 10% alcoholic water oxidizing lye solution of ϋ¾, the dicarbonic acid obtained by acidification with hydrochloric acid is treated with acetyl chloride 10 Om 1 and purified by silica gel column chromatography to obtain the following formula Π— ( 12 g of the acid anhydride of 1) was obtained.

In the following L, in a three-neck flask containing 5 g (1 Immo 1) of the above hydrate, 0.9 g of sodium hydride and tetrahydrofuran, 2.7 g (22 mmo 1) of the aniline compound of the following formula (1)

The mixture was refluxed under a nitrogen atmosphere for 4 hours. After the trace, the reaction mixture was put into a 10% salt solution, and extracted with getyl ether. The solvent was removed, the residue was dissolved in dichloromethane, 2.3 g (1 Immo 1) of dicyclohexylcarpoimide was added, and the mixture was stirred at room temperature for 3 hours. Purification by silica gel column chromatography ('dish dichloromethane) and heating of the obtained compound in o-dichloronorbenzene at 170 ° C for 0.5 hour give the following fulgimidized compound ^ JI- (1). Transposed. This ί ^^ / was purified by silica gel column chromatography using a mixed solution of hexane and black form as a liquid, and was obtained in 17% yield as pale yellow granular crystals from isobrovir alcohol and toluene. Was. ! This reduction ^ elemental analysis values C74.90% of, H5.50%, N 5.03%, 08.88%, a S5.17%, 〇 _34: ^ ₂ 0 Aru in the calculated value for the ₅ 3 Ji 74.70 %, H 5.53%, N5.12%, 08.78%, S 5.86%. When the Bronton nuclear ^^ resonance spectrum was measured (Fig. 1), the peak of 9H based on an aromatic proton was observed around 57.0 to 7.5ppra, and the peak of 3H based on the proton of the 4-position methinole group at <53.8ppm, (3H peak based on the proton of the methoxy group at the 4'-position at 52.6 ppm, (1H peak based on the 1-5 translocated proton at 54.0 ppm, 2-adamantylidene at 51.5-3.8 ρρπι) 14Η based Showed a beak.

Further ¹³ was measured C- nuclear ¾ lambda Nasupe vector 3 C- NMR), δ2 Ί~Ί O pm near the 2-Adamanchiriden group peak based on the carbon of carbon, methyl group near [delta] 1 5.7 ppm A peak based on carbon, a beak based on an aromatic carbon near S110 to 16 Opra, a beak based on carbon with> C = 0 bond near S160 to L70 ppm were shown.

 From the above results, it was confirmed that the isolate was a fulgimidated ^ II- (1) represented by the following structure.

Iron example 2-14

 Various fulgimide compounds represented by the following structural formulas I-1 (2) to I-1 (14) are obtained by synthesizing the acid anhydride of the above-mentioned formula (Π) and the aniline compound of (ΠΙ) as raw materials for synthesis. (2) to (11) Compounds were synthesized in the same manner as in Example 1, except that they were changed to those corresponding to (14).

From the results of 分析 ^ analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum measurement of the obtained compound in the same manner as in Example 1, the structure shown below was obtained as it ^ I-(2) ~ 1— The transformation shown in (14) ^! I stumbled. Table 1 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of each compound, and the characteristic chemical shifts and proton numbers of the proton nucleus spectrum. ι- (2)

LSP0 / L6d £ / 13d

pitezm OAV O SAV Mon 9s! Dd Dimension

The abbreviations and compound names of the compounds used in the following examples will be described.

 I. Polymerizable monomer

 3PG: Tripropylene glycol dimethacrylate (trade name: NK ester 3PG, Shin-Nakamura Chemical Co., Ltd.)

3G: Triethylene glycol dimethacrylate (trade name: NK ester 3G, Shin Nakamura Chemical Co., Ltd.

 4G: Tetraethylene glycol dimethacrylate (trade name: NK ester 4G, Shin-Nakamura Chemical Co., Ltd. ¾J¾)

 BPE-100N: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (trade name: NK ester BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.)

BR-MA: 2,2-bis (4-methacryloyloxytoxy 2,5-jib mouth mofenil) propane

 MS: -methylstyrene

 MSD: α-methylstyrene dimer

ΗΕΜΑ: 2-hydroxyethyl methacrylate

 Β ζΜΑ: Benzyl methacrylate

 GMA: Glycidyl methacrylate

 Π. Radical polymerization initiator

Perbutyl ND: t-butyl vinyloxy neodecaneate (trade name: Perbutyl ND, Nippon Oil Tsukisho Co., Ltd.)

Bar octa 0: 1,1,3,3-tetramethylbutinolepropoxy-1-ethynolehexanate (trade name: Bar octa 0, NOF Corporation ^ iM)

m. Chromen ^ 5

 (1) Spiro (norbornane-1,2 '-(2H) benzo (h) chromene) (2) Spiro (bicyclo [3.3.1] nonane-1,2,1,1- (2H) benzo (h) chromene)

(3) 7'-methoxyspiro (bicyclo (3.3.1) nonane-1,2,2 '-(2H) benzo (h) chromene) (4) 7'-Methoxyspiro (norbornane-1,2 '-(2H) benzo (h) chromene)

 (5) 2,2-dimethyl-7-octoxy (2H) benzo (f) chromene

 (6) 2,2- (2 * -difuryl) (2H) benzo (f) chromene

 (7) 2, 2— (Feneru 2'-furinole) (2H) benzo (f) chromene

 (8) 9-Morpholinol 2,2-bis (3-fluoro-4-methoxyphenyl (2H) benzo) chromene

 (9) 2,2- ((2,1- (3'-Fluoronaphthyl) -1-2'-Chenyl) (2H) benzo (f) chromene

IV. Spiroxazinated ^

 (1) ,, 5'-Dimethyl-6'-fluoro-6 "-morpholinodispiro (cyclohexane-1,3 '-(3H) India 1-ru 2'-(2H), 3"-(3H) (3,2-a) (1.4) oxazine

 (2) 6'-Fluoro-methoxycarbenylethyl 8 "-Methoxy-6" -Piberidinodispiro (cyclohexane-1,3 '-(3H) Indole-2'-I (2H), 3 "-I (3H) Naphtho (3,2-a) (1,4) oxazine

 (3) —Isoptyl-5 ′ —Methyl-6 ′ —Fluoro-6 ″ —Morpholinodisubiro (cyclohexane-1,3 ′ ― (3H) India 1 一 2,1 (2H), 3 ”1 (3H) naphtho (3,2-a) (1.4) oxazine

V. Flugimide compound of the present invention] ^

Transformation of the following H (A)-(F) ^ J

(A)

LSP0 / L6dT / lDd

6Z786 OAV VI. UV absorber {hereinafter abbreviated as UVA. }

Tinuvin P: 2- (5-methyl-2-hydroxyphenyl) benzotriazole

(Nippon Ciba Geigy—Shelf Inc.)

W. UV stabilizer

(1) SANOL LS-2626 (Product name: 3 ^ Μ)

(2) Mark LA-87 (Product name: Ade force 'Argasne: h)

(3) Irgas Tab 2002 (Product Name: Ciba Geigy)

Ni

(4) Mark LA-93 (trade name: Adeiki.a-gas)

(5) Shimasobu 044 (Product name: Chiba Geigine ± ¾)

Fiber example 15

 100 parts by weight of a heavy monomer composed of 45 parts by weight of 4G, 45 parts by weight of 3PG, 9 parts by weight of GMA and 1 part by weight of MSD, 0 to 05 parts by weight of fulgimide compound I (1) And 1 part by weight of perbutyl ND as a polymerization catalyst, and the mixture was thoroughly stirred until completely dissolved. This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and the mixture was heated in an air oven at 35 to 90 ° C for 20 hours to polymerize. After the polymerization, the photochromic cured product was removed from the glass plate.

A xenon lamp L-1480 (3 OOW) SHL-100 made by Hamamatsu Photonics was applied to the obtained 2 mm thick photochromic cured product through an air port mass filter (coining recitation) at 20 ° C ± 1 ° C. 36511111 = 2.411 ^ ¥ / cm ²

The color was developed by irradiating for 20 seconds, and the value of ε (120 seconds) -ε (0 seconds) was determined, and the result was defined as color-acid. However, epsilon (120 seconds) is the absorbance of light irradiation after 120 seconds at the maximum absorption wavelength, _£ (0 seconds) is the absorbance of the maximum absorption wavelength during light unirradiated ₀

 Fatigue life was measured using a xenon long life feed meter FAL-125 HC from Suga Machinery Co., Ltd. Fatigue life (T1 / 2) is changed to Fulgimid ^! The color development ^^ was expressed as the time required for the color to drop to the initial 12. Table 2 shows the results.

鵷 Example 16-28

The fulgurimidization (2)-11 (14) A photochromic cured product was prepared in the same manner as in 15, and the color development and the fatigue life were measured. The results are shown in Table 2.

Fiber example 2 9 ~ 3 2

 Example 15 was carried out in the same manner as in Example 15 except that the composition of the polymerizable monomer in Table 15 was changed. The results are shown in Table 2.

Comparative Examples 1 to 6

For the purpose of comparison, a fumed tochromic cured product was prepared in the same manner also for the compounds represented by fulgimidated ^ I (A) to (F) other than the present invention, and the coloring density and fatigue life were measured. The results are shown in Table 2.

8 9L / 6 OAVdi71: £ 1

From the results in Table 2, it can be seen that the fulgimide compound of the present invention has a higher color transfer power and a higher power than the conventional fulgimide compound.

Crane example 33

 In Example 15, a photochromic cured product was obtained in the same manner as in Example 15 except that 0.05 parts of (1) SANOL LS-2626 was added as ultraviolet rays. The obtained cured product was measured in the same manner as in Example 15. Table 3 shows the results.

Difficult case 34-46

 行 っ Example 33 was carried out in the same manner as in Example 33 except that the fulgimide compound and the ultraviolet stabilizer of the present invention were changed. Table 3 shows the results.

 From the results in Table 3, it can be seen that the fatigue life was improved by the addition of the UV stabilizer compared to the examples in Table 2. Table 3

 Example NO Flumidamide NO UV stabilizer T1 / 2 (hour)

 NO addition amount (parts by weight)

 33 I- (1) (1) 0.05 150

34 I- (Ί) (1) 1.0 255

35 I- (1) (2) 0.5 174

36 I- (1) (3) 0.4 165

37 I- (1) (4) 0.7 180

38 I-(1) (5) 0.5 188

39 I-(2) (1) 0.05 166

40 ι- (2) (2) 1.0 189

41 I-(2) (5) 0.5 206

42 I-(3) (1) 0.5 403

43 I- (3) (2) 0.7 408

44 I- (3) (3) 0.7 411

45 I-(4) (1) 0.5 166

46 ι- (4) (2) 2.0 234 Example of fiber 47

 H! Same as Example 15 except that in Example 15, the photochromic ^ / was changed to 0.04 part of chromene compound (2), 0.03 part of fulgimide compound I- (1) of the present invention, and 0.05 part of spiroxazinated ^ (1). In this manner, a photochromic sclero was obtained.

 The resulting photochromic cured product was evaluated for color development density and color shift after prolonged use.

First, a xenon lamp L-1 2480 (300W) SHL-100 manufactured by Hamamatsu Photonics was applied to the photochromic cured product before use at 20 ± 1 ° C through an air port mass filter (manufactured by Koingen Co.) at 20 ± 1 ° C. The beam was irradiated with light at a beam key of 3 65 nm = 2.4 mW / cm ² _> 254 nm = 24 WZcm ² for 120 seconds on the surface of the cured product, and the initial color spectrum (To) was measured.

Thereafter, the photochromic cured product was irradiated with sunlight for 30 minutes to develop a color, and then subjected to a cycle of fading with fluorescence for 1 hour three times a day for a total of 30 days. In the same manner as before the photochromic cured body after ^^ was measured the initial color scan Bae-vector (T _30).

In T ₀ and T ₃₀ each color scan base spectrum, the absorbance at the maximum absorption wavelength in the maximum absorbance of the absorption wavelength and five hundred and eighty to five hundred ninety nm at 450-470 nm was determined, respectively. The absorbance at the maximum absorption wavelength of 450 to 47011111 indicates the color density of ¾ ^, and the absorbance at the maximum absorption wavelength of 580 to 590 nm indicates the color density of fe. Based on these measured values, the color density and color shift defined below were determined.

Initial color density (Abs.) = T . _: Blue color density at.

 Color shift (%) = Other durability (%) — Blue durability (%)

 In the above 2¾, the durability of yellow and the durability of ½ are the values defined below.

Yellow durability (%) = Yellow color density at T ₃₀ Yellow color density at TTC, X 100 Blue durability (= Blue color density at T ₃ ./Blue color density at T. X100 also the to and T ₃₀ each Fotoku port Mitsuku hardness I human body were developed by sunlight, the The coloring of time fe! S was visually Nffi. As a result, the initial color development was 0.88, and the color shift was 5%. Table 4 shows the results.

麵 Example 4 8-5 5

 In Example 47, chromene formation ^ /, fulgimidation of the present invention ^ /, spiroxazination ^! The procedure was performed in the same manner as in Example 47, except that the ultraviolet absorber was changed to haze as shown in Table 4. Table 4 shows the results.

Fiber example 5 6

 Example 4 7 except that the composition of the polymerizable monomer was changed to 4 G 60 parts, 3 G 15 parts, HEMA 5 parts, GMA 10 parts, MS 9 parts and MSD 1 part in Example 47. The same was done. Table 4 shows the results.

Difficult case 5 7-6 1

 Example 56 was carried out in the same manner as in Example 56, except that the composition was changed to the composition shown in Table 4, except that the chromene formation, the fulgimidation of the present invention, the spiroxazine compound and the ultraviolet absorber were changed. Table 4 shows the results.

Comparative Examples 7 and 8

 Using the known fulgimide compounds (F) and (D) without using the fulgimide compound of the present invention, the initial colored fiber and color shift were determined for the yarn shown in Table 4 in the same manner as in Example 47. . Table 4 shows the results.

 Comparing Example 47 of the present invention with Comparative Example 7, Example 47 using the fulgimide compound of the present invention shows that flugimidinated ^! It can be seen that the color development equivalent to that of Comparative Example 7 can be obtained even though the blending amount of is less than 1 Z2.

In Comparative Example 8, in which the blending amount of the fulgimide compound was the same as in Fiber Example 47, the initial color development was about half that in Example 47. Table 4

Example Chromene Compound Flugimide Compound (Invention) Spiroxazine Compound UVA

 No Addition amount (parts) No Addition amount (parts) No Addition amount (parts) No Addition amount (parts)

47 (2) 0.04 I-(1) 0.03 (1) 0.05

48 (2) 0.045 I-(1) 0.05 (1) 0.05--

49 (2) 0.05 I-(1) 0.03 (1) 0.07

 50 (2. »/ V3.) 0.02 / 0.055 ι- (2) 0.025 (1) 0.05

 51 (1. (.) 0.02 / 0.05 ι- (3) 0.025 (1) 0.05

 52 (5) 0.06 I-(4) 0.03 (2) 0.04

 53 (8) 0.025 ι- (1) 0.025 (1) 0.05

54 (8.¾.) 0.02 / 0.05 ι- (8) 0.025 () 0.03 ―

55 (2) 0.07 I-(1) 0.03 (1) 0.05 1 0.03

56 (2) 0.07 I-(1) 0.03 (1) 0.05--

57 (8) 0.025 I-(1) 0.025 (1) 0.05-one

 58 (6) 0.05 I-(5) 0.03 (1) 0.04

 59 (8) 0.05 I-(1) 0.05 (1) 0.1

 60 (7) 0.03 I-(8) 0.03 (3) 0.03

 61 (2) 0.07 ι- (1) 0.03 (1) 0.05 1 0.03 Comparative example Chromene compound Known flugimide compound Spirooxazine compound UVA

 No addition amount (parts) No addition amount (parts) No addition amount (parts) No addition amount (parts)

7 (2) 0.05 (F) 0.07 (1) 0.055

8 (2 o.) 0.015 / 0.035 (F ©.) 0.015 / 0.015 (1) 0.05

Table 4 (continued)

 Around |

Example TO color tone Initial color density T30 color tone Color fading Fulgimit Spiroxacin

 (Abs.) (%) Weight ratio

 Cray 0.88 Clay 5 0.60

48 clay 1.15 clay 10 1.00

 49 Cray 0.92 Pray 3 0.43

 50 fans 0.83 fans 5 0.50

 51 FUNO 0.86 FUNN 5 0.50

 52 fans 0.84 fans 7 0.75

 53 clay 0.82 clay 5 0.50

 54 fans 0.81 fans 7 0.67

 55 Clay 0.90 Kure 0 0.60

 56 Gueret 0.90 Kurray 4 0.60

 57 Clay 0.83 Kure 6 0.50

Do '; A ,, 1 ♦ A, ·

 Nofwano U.O One

 Fuwano 8 0./D

 59 Kle-1.20 Gel-7 0.50

 60 Brown 0.90 Van 7 1.00

 61 Gere-0.93 Gere-2 0.60

Comparative example TO color tone Initial color density T30 color tone Color shift Flugimide Spiroxazine

 (Abs.) ()

 7 Gueret-0.82

8 Fraun 0.42

Male 62

 In Example 47, the polymerizable monomer used was BPE-10 ON 70 parts, BzMA 20 parts, GMA 9 parts, MSD 1 part, and the polymerization catalyst used was perbutyl N DZ powder 0 = 0/5 / 0.4 weight The same procedures as in Example 47 were performed, except that the parts were changed. As a result, the initial color density was 0.86, and the color shift was 6%.

鵷 Example 63-70

Chromening in Example 62 ^! , Of the present invention ^! The measurement was carried out in the same manner as in Example 62, except that the compositions of the spiroxazine compound and the ultraviolet absorber were changed as shown in Table 5. Table 5 shows the results.

Example Chromene compound Flugimide compound Spirooxazine compound UVA

 No addition amount (part) No addition amount (part) No addition amount (part) No addition amount (part)

62 (2) 0.04 I-) 0.03 (1) 0.05

 63 (2> 0.045 ι- (1) 0.05 (1) 0.05

 64 0.05 I-(1) 0.03 (1) 0.07

 65 (2.X6.) 0.02 / 0.055 I-(2) 0.025 (1) 0.05

 66 (i) 0.02 / 0.05 I-(3) 0.025 (1) 0.05

 67 (5) 0.06 ι- (4) 0.03 (2) 0.04

 68 (6) 0.05 I-(5) 0.03 (1) 0.04

 69 (8) 0.05 I-(1) 0.05 (1) 0.1

70 (2) 0.07 ι- (1) 0.03 (1) 0.05 1 0.03

Table 5 (continued)

Example TO color tone Initial color density T30 color tone Color shift fulgimidspiroxazine

 (Abs.) (%) Weight ratio

 62 Gueret 0.86 Gueret-6 0.60

 63 Gueret-1.20 Gueret-5 1.00

 64 pieces-0.89 pieces-2 0.43

 65 Brown 0J9 House 2 0.50

 66 Raun 0.85 Hua Raun 2 0.50

 67 Brown 0.86 "Round 5 0J5

 68 inches 0.82 inches 2 0J5

 69 Gueret-1.22 Guerre-1 0.50

70 pieces-0.93 pieces--3 0.60

BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a chart of the ^ ギ —nuclear magnetic spectrum of fulgimidization obtained in Example 1.

Claims

The scope of the claims

The following "^ Fullimidization represented by formula (I) ^

[In the formula, the following group (a) is a divalent hydrogenated aromatic group or a divalent unsaturated heterocyclic group which may have a substituent,

The following groups (b) are a norbornylidene group, a bicyclo [3.3.1] nonylidene group or an adamantylidene group, each of which may have a substituent;

("(b)

R ¹ is a monovalent carbon group or a monovalent heterocyclic group which may have a substituent,

R ² is an electron withdrawing group,

R ³ is an alkyl group, aryl group, amino group, alkoxy group or electron withdrawing group, n is an integer of 0 to 4, and when n is an integer of 2 or more, R ⁵ is a different atom Or you can be radical. ]

 2. The fulgimidate according to claim 1, wherein in the general formula (I), the group (a) is a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

3. In the general formula (I), the group (a) is a 5- or 6-membered monocyclic unsaturated heterocyclic group containing 1 to 3 atoms of at least one of a nitrogen atom, an oxygen atom and an iodine atom. Ring or condensed unsaturated bicyclic ring condensed with benzene ring or cyclohexene ring 2. The fulgimide compound according to claim 1, which is a divalent unsaturated heterocyclic group selected from elementary rings.

 4. In the general formula (I), the group (a) is a halogen atom, a nitro group, a cyano group, an amino group, an alkynole group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Are substituted by 1 to 3 atoms or groups selected from the group consisting of an alkylthio group, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 7 to 15 carbon atoms. The fulgimide compound according to claim 1, which is a divalent fragrance; a ^ it * elemental group, or a divalent unsaturated heterocyclic group.

 5. In the formula (I), the group (a) is a halogen atom, a nitro group, a cyano group, an amino group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,

A nitrogen atom which may be substituted by 1 to 3 atoms or groups selected from the group consisting of an alkylthio group having 4 to 4, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms. 2. The fulgimide compound according to claim 1, which is a 5- or 6-membered divalent monocyclic heterocyclic group having one atom, oxygen atom or y-atom.

6. The fulgimide compound according to claim 1, wherein in the formula (I), the group (b) is an adamantylidene group which may have a substituent.

7. In the formula (I), R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 6 to 6 carbon atoms, each of which may have a substituent. L 4 aryl group or carbon number? The fulgimide according to claim 1, which is an aralkyl group of 1 to 10.

8. The said ^ formula (I), wherein R ¹ is an alkynole group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 weaves, each of which may have an MM group. Flugimide compounds.

9. In the formula (I), R ² represents a halogen atom; a perhalogenoalkyl group; a cyano group; an optionally substituted alkoxycarbonyl group; A diaryl group; an arylcarbonyl group which may have a substituent; a nitro group; a sulfonyl group; an alkylsulfonyl group which may have a substituent; An arylsulfonyl group; or having a substituent 2. The fulgimide compound according to claim 1, wherein the fulgimide compound is a carboxyloxycarbonyl group.

10. In the general formula (I), R ³ is an alkyl group having 1 to 6 carbon atoms; an aryl group having 6 to 14 carbon atoms; an alkylamino group having 1 to 5 carbon atoms; An alkoxy group; a halogen atom; a perhalogenoalkyl group; a cyano group; an alkoxycarbonyl group which may have a substituent; an alkylcarbonyl group which may have a substituent; Good arylcarbonyl group; nitro group; sulfonyl group; optionally substituted alkylsulfonyl group; optionally substituted arylsulfonyl group; or optionally substituted The fulgimide compound according to claim 1, which is a good aryloxycarbonyl group.

11. In the formula (I), n is 0, R ¹ is an alkyl group or a cycloalkyl group which may have a substituent, and the electron-withdrawing group represented by R ² is a halogen atom. Atom, perhalogenoalkyl group, cyano group, alkoxycarbonyl group optionally having substituent (s), alkylcarbonyl group optionally having substituent (s), aryl group (s) optionally having substituent (s) A carbonyl group, a nitro group, a sulfonyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, or a group having a substituent. 2. The fulgimidate according to claim 1, wherein the fulgimiyl group is a radicaloxycarbonyl group; Compound.

 1 2. A photochromic material comprising the fulgimidized compound of claim 1.

 1 3. A polymerizable photochromic pirates comprising 100 parts by weight of heavy monomer and 10.0 parts by weight of fulgimidinated according to claim 1.

 1 4. The polymerizable monomer is composed of 100 parts by weight of a radical polymerizable monomer and 1 to 30 parts by weight of a heavy ft monomer having at least one epoxy group in one molecule. Claim 1 3 A self-loaded heavy photochromic product.

 15. The weight of claim 13, further comprising 0.01 to 0.2 parts by weight of each of the chromene-containing kiss and / or the spiroxazine-containing kiss based on 100 parts by weight of the polymerizable monomer. 14 Photochromic $ Castle.

1 6. Further, the UV stabilizer was converted to fulgimidation ^ 0.01 to 100 parts by weight. 14. The polymerizable photoglomic yarn according to claim 13, comprising a looo osa part.

17. (1) Radican cane heavy monomer 100 parts by weight and heavy monomer having 1 to 30 parts by weight of a heavy ft monomer having at least one epoxy group in one molecule, and

 (2) Foreword Based on 100 parts by weight of the monomer, 0.01 to 0.05 part by weight of the fulgimide compound according to claim 1, 50.01 to 0.2 part by weight of chromene and 5.03 to 0.1 part by weight of spirooxazine are contained. 14. The heavy photomixture according to claim 13, wherein the weight ratio of fulgimide compound / spiroxazine compound ^ I is 1 or less.

18. A photochromic lens comprising a polymer formed from the above-mentioned 13-year-old tochromic thread material.